WO2007029828A1 - Procédés d'analyse, d’exposition et de fabrication de dispositif - Google Patents

Procédés d'analyse, d’exposition et de fabrication de dispositif Download PDF

Info

Publication number
WO2007029828A1
WO2007029828A1 PCT/JP2006/317901 JP2006317901W WO2007029828A1 WO 2007029828 A1 WO2007029828 A1 WO 2007029828A1 JP 2006317901 W JP2006317901 W JP 2006317901W WO 2007029828 A1 WO2007029828 A1 WO 2007029828A1
Authority
WO
WIPO (PCT)
Prior art keywords
substrate
exposure
liquid
film
abnormality
Prior art date
Application number
PCT/JP2006/317901
Other languages
English (en)
Japanese (ja)
Inventor
Katsushi Nakano
Original Assignee
Nikon Corporation
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nikon Corporation filed Critical Nikon Corporation
Priority to JP2007534489A priority Critical patent/JP4992718B2/ja
Publication of WO2007029828A1 publication Critical patent/WO2007029828A1/fr

Links

Classifications

    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/70—Microphotolithographic exposure; Apparatus therefor
    • G03F7/70216—Mask projection systems
    • G03F7/70341—Details of immersion lithography aspects, e.g. exposure media or control of immersion liquid supply

Definitions

  • the present invention relates to an analysis method, an exposure method, and a device manufacturing method for analyzing an exposure failure of a substrate exposed through a liquid.
  • an immersion exposure apparatus In an exposure apparatus used in the photolithography process, an immersion exposure apparatus has been devised that exposes a substrate through a liquid as disclosed in the following patent document.
  • Patent Document 1 Pamphlet of International Publication No. 99Z49504
  • the present invention adopts the following configuration associated with each drawing shown in the embodiment.
  • the reference numerals with parentheses attached to each element are merely examples of the element and do not limit each element.
  • the developing step (SA60) for developing the substrate (P) in the analysis method for analyzing the exposure failure of the substrate (P) exposed through the liquid (LQ), the developing step (SA60) for developing the substrate (P) ), The first measurement process (SA50) for measuring abnormalities of the substrate (P) before development, and the substrate after development (SA50) Based on the measurement result of the second measurement process (SA70), the first measurement process (SA50) and the measurement result of the second measurement process (SA70)! And an analysis step (SA80) for analyzing an exposure failure of the substrate (P) exposed through the substrate.
  • the exposure method for exposing the substrate (P) through the liquid (LQ) includes the step of analyzing the state of the substrate (P) by the analysis method of the above aspect. An exposure method is provided.
  • the substrate can be satisfactorily exposed using the result of analyzing the exposure failure of the substrate.
  • the outermost layer of the substrate (P) is formed before the exposure of the substrate (P).
  • An exposure method is provided that obtains the relationship between the receding contact angle of the liquid (LQ) on the film (eg, Tc) to be exposed and the defect level of the substrate after exposure.
  • the substrate can be satisfactorily exposed using the relationship between the receding contact angle of the liquid and the defect level of the exposed substrate.
  • a device can be manufactured using an exposure method capable of satisfactorily exposing a substrate.
  • FIG. 1 is a schematic block diagram that shows a device manufacturing system that includes an exposure apparatus according to a first embodiment.
  • FIG. 2 is a cross-sectional view schematically showing an example of a substrate.
  • FIG. 3 is a schematic block diagram that shows an exposure apparatus according to the first embodiment.
  • FIG. 4 is a diagram for explaining an immersion system.
  • FIG. 5 is a diagram for explaining an example of a positional relationship between a liquid immersion region and a substrate stage holding a substrate.
  • FIG. 6 is a schematic diagram for explaining an example of an abnormality occurring in a film.
  • FIG. 7 is a schematic diagram for explaining an example of an abnormality occurring in a film.
  • FIG. 8 is a schematic diagram for explaining an example of an abnormality occurring in a film.
  • FIG. 9 is a schematic diagram for explaining an example of an abnormality occurring in a film.
  • FIG. 10 is a schematic diagram for explaining an example of an abnormality occurring in a film.
  • FIG. 11 is a schematic diagram for explaining an example of an abnormality occurring in a film.
  • FIG. 12 is a flowchart for explaining the analysis method according to the first embodiment.
  • FIG. 13 is a diagram for explaining a measurement process for measuring a substrate abnormality.
  • FIG. 14A is a diagram showing an example of an optical image obtained by measurement processing.
  • FIG. 14B is a diagram showing an example of an optical image obtained by measurement processing.
  • FIG. 15A is a diagram showing an example of an optical image obtained by measurement processing.
  • FIG. 15B is a diagram showing an example of an optical image obtained by measurement processing.
  • FIG. 16 is a flowchart for explaining an analysis method according to the second embodiment.
  • FIG. 17 is a view for explaining a receding contact angle according to the third embodiment.
  • FIG. 18 is a diagram showing the relationship between the receding contact angle of liquid on the substrate surface and the defect level.
  • FIG. 19 is a flowchart for explaining an example of a microdevice manufacturing process.
  • FIG. 1 is a view showing a device manufacturing system SYS provided with the exposure apparatus EX according to the first embodiment.
  • the device manufacturing system SY S includes an exposure apparatus EX and a coater / developer apparatus CD connected to the exposure apparatus EX.
  • the exposure apparatus EX has a mask stage 3 that can move while holding the mask M, and a substrate holder 4H that holds the substrate P.
  • the substrate stage that can move while holding the substrate P in the substrate holder 4H. 4 and the illumination optical system IL that illuminates the mask M held by the mask stage 3 with the exposure light EL, and the projection optical system that projects the pattern image of the mask M illuminated with the exposure light EL onto the substrate P.
  • PL and a control device 7 for controlling the overall operation of the exposure apparatus EX are provided.
  • a scanning exposure apparatus that exposes a pattern formed on mask M onto substrate P while synchronously moving mask M and substrate P in the scanning direction.
  • the synchronous movement direction (scanning direction) of the mask M and the substrate P in the horizontal plane is the Y axis direction
  • the direction orthogonal to the Y axis direction is the X axis direction (non-scanning).
  • Direction perpendicular to the X-axis and Y-axis directions and parallel to the optical axis
  • AX of the projection optical system PL is defined as the Z-axis direction.
  • the rotation (tilt) directions around the X, Y, and Z axes are the 0 X, 0 Y, and 0 Z directions, respectively.
  • the exposure apparatus EX of the present embodiment is an immersion exposure apparatus to which an immersion method is applied in order to substantially shorten the exposure wavelength to improve the resolution and substantially increase the depth of focus. .
  • a liquid LQ immersion area LR is formed on the substrate P held by the substrate stage 4, and the exposure light EL is irradiated onto the substrate P through the liquid LQ in the immersion area LR. Then, the substrate P is exposed.
  • water pure water
  • the coater / developer apparatus CD includes a coating apparatus for coating a predetermined film on the base material of the substrate P before the exposure process, and a developer apparatus for developing the substrate P after the exposure process.
  • the exposure apparatus EX and the coater / developer apparatus CD are connected via an interface IF.
  • the substrate P can be transported between the exposure apparatus EX and the coater / developer apparatus CD via an interface IF by a transport apparatus (not shown).
  • FIG. 2 is a view showing an example of a substrate P including a base material on which a predetermined film is coated by a coating device for a coater / developer apparatus CD.
  • the substrate P is a semiconductor wafer.
  • a first lHRg coated on the substrate W and a second film Tc coated on the first HRg.
  • the lHRg is a film that also has a photosensitive material (photoresist) force.
  • the second film Tc is a film called a top coat film, and has a function of protecting the lHRg substrate W, which also serves as a photosensitive material, from the liquid LQ, and is repellent to the liquid LQ. It has liquidity (water repellency).
  • the second film Tc which is a liquid repellent film, it is possible to improve the recoverability of the liquid LQ.
  • the first lHRg is formed by applying a photosensitive material (photoresist) on the substrate W by, for example, a spin coating method.
  • the second film Tc is formed by applying a material for forming the topcoat film. Since the liquid LQ immersion area LR is formed on the second film Tc of the substrate P, a liquid contact surface of the substrate P that contacts the liquid LQ of the second film Tc force immersion area LR is formed.
  • FIG. 3 is a schematic block diagram that shows the exposure apparatus EX according to the present embodiment.
  • the exposure apparatus EX includes an immersion system 1 that fills the optical path space K of the exposure light EL near the image plane of the projection optical system PL with the liquid LQ to form an immersion area LR.
  • the operation of the immersion system 1 is controlled by the controller 7.
  • the immersion system 1 is a substrate disposed on the lower surface of the final optical element FL closest to the image plane of the projection optical system PL and the image plane side of the projection optical system PL among the plurality of optical elements of the projection optical system PL.
  • An immersion region LR is formed on the substrate P so that the optical path space K of the exposure light EL between the surface of the substrate P on the holder 4H and the liquid LQ is filled with the liquid LQ.
  • the exposure apparatus EX projects at least the pattern image of the mask M onto the substrate P, and fills the optical path space K of the exposure light EL with the liquid LQ using the liquid immersion system 1 during the period.
  • the exposure apparatus EX irradiates the exposure light EL passed through the mask M onto the substrate P held by the substrate holder 4H via the projection optical system PL and the liquid LQ filled in the optical path space K of the exposure light EL.
  • the pattern image of the mask M is projected onto the substrate P, and the substrate P is exposed.
  • the exposure apparatus EX of the present embodiment has a liquid LQ force filled in the optical path space K of the exposure light EL between the final optical element FL and the substrate P.
  • a partial liquid immersion method in which a liquid LQ liquid immersion area LR that is larger than the projection area AR and smaller than the substrate P is locally formed in a part of the area is adopted.
  • the immersion region LR is not only on the substrate P, but also on the image plane side of the projection optical system PL. It can also be formed on an object disposed at a position facing the lower surface of the final optical element FL, for example, a part of the substrate stage 4.
  • the illumination optical system IL illuminates a predetermined illumination area on the mask M with exposure light EL having a uniform illuminance distribution.
  • the exposure light EL that also emits IL force includes, for example, bright lines (g-line, h-line, i-line) and KrF excimer laser light (wavelength 248nm) that also emit mercury lamp force (DUV light).
  • ArF excimer laser light wavelength 193nm
  • F laser light (wavelength 193nm)
  • Vacuum ultraviolet light such as 2 wavelengths (157 nm) is used.
  • ArF excimer laser light is used.
  • the mask stage 3 is movable in the X axis, Y axis, and ⁇ Z directions while holding the mask M by driving a mask stage driving device 3D including an actuator such as a linear motor.
  • the position information of mask stage 3 (and hence mask M) is measured by laser interferometer 3L.
  • the laser interferometer 3L measures the position information of the mask stage 3 using a moving mirror 3K provided on the mask stage 3.
  • the control device 7 drives the mask stage drive device 3D based on the measurement result of the laser interferometer 3L, and controls the position of the mask M held on the mask stage 3.
  • the mask here includes a reticle on which a device pattern to be reduced and projected on a substrate is formed.
  • a force reflection type mask using a transmission type mask as a mask may be used! ,.
  • the movable mirror 3K may include not only a plane mirror but also a corner cube (retroreflector). Instead of fixing the movable mirror 3K to the mask stage 3, for example, the end surface (side surface) of the mask stage 3 may be used. ) May be used as a reflecting surface formed by mirror finishing. Further, the mask stage 3 may be configured to be capable of coarse and fine movement disclosed in, for example, JP-A-8-130179 (corresponding US Pat. No. 6,721,034).
  • the projection optical system PL projects a pattern image of the mask M onto the substrate P at a predetermined projection magnification, and has a plurality of optical elements, and these optical elements are held by a lens barrel PK. ing.
  • the projection optical system PL of the present embodiment is a reduction system whose projection magnification is, for example, 1Z4, 1/5, 1/8, etc., and forms a reduced image of the mask pattern in the projection area AR conjugate with the illumination area described above. .
  • the projection optical system PL may be any of a reduction system, a unity magnification system, and an enlargement system.
  • the projection optical system PL includes a refractive system that does not include a reflective optical element and a refractive optical element. Any reflective system including a reflective optical element including a reflective optical element and a refractive optical element may be used. Further, the projection optical system PL may form either an inverted image or an erect image.
  • the substrate stage 4 has a substrate holder 4H that holds the substrate P, and is driven by a substrate stage driving device 4D that includes an actuator such as a linear motor, while holding the substrate P on the substrate holder 4H.
  • a substrate stage driving device 4D that includes an actuator such as a linear motor
  • the substrate holder 4H is disposed in a recess 4R provided on the substrate stage 4, and the upper surface 4F of the substrate stage 4 other than the recess 4R is substantially the same height as the surface of the substrate P held by the substrate holder 4H.
  • the surface is flat.
  • a part of the liquid immersion region LR protrudes from the surface of the substrate P and is formed on the upper surface 4F.
  • a predetermined region surrounding the substrate P may be substantially the same as the surface of the substrate P.
  • the optical path space K on the image plane side of the projection optical system PL can be continuously filled with the liquid LQ (that is, the liquid immersion area LR can be satisfactorily held)
  • the substrate P held by the substrate holder 4H is supported. There may be a step between the surface of the substrate and the upper surface 4F of the substrate stage 4.
  • the substrate holder 4H may be formed integrally with a part of the substrate stage 4.
  • the substrate holder 4H and the substrate stage 4 are configured separately, for example, by vacuum suction or the like. Fix 4H to recess 4R.
  • the position information of the substrate stage 4 (and hence the substrate P) is measured by the laser interferometer 4L.
  • the laser interferometer 4L uses the movable mirror 4K provided on the substrate stage 4 to measure position information of the substrate stage 4 in the X axis, Y axis, and ⁇ Z directions.
  • the surface position information of the surface of the substrate P held on the substrate stage 4 (position information regarding the Z axis, ⁇ X, and ⁇ Y directions) is obtained by a focus leveling detection system (not shown). Detected.
  • the control device 7 drives the substrate stage driving device 4D based on the measurement result of the laser interferometer 4L and the detection result of the focus / leveling detection system, and controls the position of the substrate P held on the substrate stage 4. I do.
  • the details of the laser interferometer 4L that can measure the position of the substrate stage 4 in the Z-axis direction and the rotation information in the 0 X and 0 Y directions are also described in, for example, JP 2001-510577 A Corresponding to International Publication No. 1999Z28790 pamphlet).
  • moving mirror instead of fixing 4K to the substrate stage 4, for example, you can use a reflective surface formed by mirror processing a part of the substrate stage 4 (side surface, etc.)!
  • the focus / leveling detection system measures position information in the ⁇ -axis direction of the substrate ⁇ ⁇ at each of its multiple measurement points, so that tilt information (rotation information) in the ⁇ X and ⁇ ⁇ directions of the substrate (
  • the plurality of measurement points may be set at least partially within the immersion area LR (or projection area AR), or all of the measurement points may be in the immersion area LR. It may be set outside.
  • the position information in the ⁇ axis direction can be measured during the exposure operation of the substrate ⁇ .
  • the position of the substrate ⁇ is controlled in the X axis, ⁇ X and 0 0 directions using the measurement results of the laser interferometer 4L during the exposure operation. Even so,
  • FIG. 4 is an enlarged view showing the main part of FIG.
  • the immersion system 1 is an optical path space K of the exposure light EL between the final optical element FL of the projection optical system PL and the substrate P that is disposed at a position facing the final optical element FL and held by the substrate holder 4H. Is filled with liquid LQ.
  • the immersion system 1 is provided in the vicinity of the optical path space K of the exposure light EL between the final optical element FL and the substrate P, and the supply port 12 for supplying the liquid LQ to the optical path space K and the liquid
  • a liquid supply device 11 for supplying liquid LQ to the supply port 12 via a nozzle member 71 having a recovery port 22 for recovering LQ, a supply pipe 13 and a supply flow path 14 formed inside the nozzle member 71
  • a liquid recovery device 21 for recovering the liquid LQ recovered from the recovery port 22 of the nozzle member 71 through the recovery flow path 24 formed inside the nozzle member 71 and the recovery pipe 23.
  • the supply port 12 and the supply pipe 13 are connected via a supply flow path 14.
  • the recovery port 22 and the recovery pipe 23 are connected via a recovery flow path 24.
  • the nozzle member 71 is provided in an annular shape so as to surround the optical path space K of the exposure light EL.
  • the supply port 12 for supplying the liquid LQ is provided on the inner surface of the nozzle member 71 facing the optical path space K of the exposure light EL.
  • the recovery port 22 for recovering the liquid LQ is provided on the lower surface of the nozzle member 71 facing the surface of the substrate P.
  • a porous member (mesh) 25 is disposed in the recovery port 22.
  • the liquid supply device 11 includes a temperature adjustment device that adjusts the temperature of the liquid LQ to be supplied, a deaeration device that reduces the gas components in the liquid LQ, and a filter unit that removes foreign matters in the liquid LQ. It is possible to deliver clean and temperature-controlled liquid LQ.
  • the liquid recovery device 21 includes a vacuum system or the like, and can recover the liquid LQ. The operations of the liquid supply device 11 and the liquid recovery device 21 are controlled by the control device 7.
  • the liquid LQ delivered from the liquid supply device 11 flows through the supply pipe 13 and the supply flow path 14 of the nozzle member 71 and then is supplied from the supply port 12 to the optical path space K of the exposure light EL.
  • the liquid LQ recovered from the recovery port 22 by driving the liquid recovery device 21 flows through the recovery flow path 24 of the nozzle member 71 and is then recovered by the liquid recovery device 21 via the recovery pipe 23.
  • the control device 7 controls the immersion system 1 to perform the liquid supply operation by the liquid supply device 11 and the liquid recovery operation by the liquid recovery device 21 in parallel, so that the final optical element FL and the substrate P are aligned.
  • the optical path space K of the exposure light EL is filled with liquid LQ, and a liquid LQ immersion area LR is locally formed in a partial area on the substrate P.
  • the upper surface of the substrate W is coated (coated) with the first lHRg made of a photosensitive material.
  • a predetermined process including a process of removing the photosensitive material such as the peripheral region and the side surface of the upper surface of the substrate W using a solvent (edge rinse process), a beta process, and the like is performed.
  • the second film Tc serving as the topcoat film on the lHRg on the substrate W is performed.
  • the second film Tc has a function of protecting the first LHRg made of the photosensitive material formed on the substrate W with the liquid LQ force.
  • edge rinse processing is performed as necessary, and then predetermined processing including beta processing is performed.
  • the substrate P is transported to the exposure apparatus EX by a predetermined transport device.
  • the exposure apparatus EX forms a liquid LQ immersion region LR on the second film Tc of the substrate P and irradiates the substrate P with the exposure light EL.
  • FIG. 5 is a view for explaining an example of the positional relationship between the immersion region LR and the substrate stage 4 holding the substrate P when the substrate P is exposed.
  • a plurality of shot regions S1 to S21 are set on the substrate P in a matrix shape.
  • the exposure apparatus EX projects and exposes the pattern of the mask ⁇ onto the substrate ⁇ ⁇ ⁇ ⁇ while moving the mask M and the substrate P in the Y-axis direction (scanning direction).
  • the control device 7 shows the projection area AR of the projection optical system PL and the liquid LQ covering it.
  • the exposure light EL is irradiated onto the substrate P through the liquid LQ in the immersion region LR while relatively moving between the immersion region LR and the substrate P.
  • the control device 7 controls the operation of the substrate stage 4 so that the projection area AR (exposure light EL) of the projection optical system PL moves along the arrow yl on the substrate P.
  • the controller 7 moves the substrate P (substrate stage 4) by stepping to move the next shot area to the exposure start position.
  • Each of the shot areas S1 to S21 is sequentially scanned and exposed while moving.
  • the exposure failure includes a defect of a pattern formed on the substrate P by exposure.
  • the cause of the exposure failure includes at least one of an abnormality of the second film Tc formed on the surface of the substrate P and a foreign matter (bubble, particle) in the liquid LQ.
  • the abnormality of the second film Tc includes a state in which the liquid LQ is infiltrated into the second film Tc, a state in which foreign matters (bubbles, particles) are present inside the second film Tc, and a part of the second film Tc is It includes at least one of a peeled state and a state in which foreign matter (particles) adheres to the second film Tc.
  • the liquid LQ in the immersion region LR contacts the second film Tc formed on the surface of the substrate P.
  • the liquid LQ in contact with the second film Tc on the substrate P may penetrate (infiltrate) into the second film Tc.
  • the liquid LQ soaked into the second film Tc exists between the lHRg and the second film Tc. In such a state, when the exposure light EL is irradiated onto the substrate P, the exposure state of the exposure light EL on the first film Rg (or the substrate W) may be changed by the soaked liquid LQ. is there.
  • the optical path of the exposure light EL may change at the interface between the second film Tc and the soaked liquid.
  • the exposure light EL changes at the interface between the second film Tc and the soaked liquid, the exposure light EL does not reach the desired position of the first film Rg, and a desired pattern image is not formed. Exposure defects such as defects in the pattern formed on the material W may occur.
  • the liquid LQ soaked inside the second film Tc and the second film There is a possibility that a part of the exposure light EL is reflected at the interface with Tc, and the first film Rg cannot be irradiated with the exposure light EL having a desired light amount (intensity). Also, the exposure light EL may be diffusely reflected by the soaked liquid LQ.
  • the shape of the second film Tc changes locally, for example, when the second film Tc swells due to the liquid LQ soaked into the second film Tc. There is also a possibility to do. Also in FIG. 7, a defect such as a change in the optical path of the exposure light EL may occur, resulting in a defective exposure such as a defect in the pattern formed on the substrate W.
  • the optical path of the exposure light EL changes due to the foreign matters (bubbles and particles). Inadequate exposure may occur, such as defects in the pattern formed on the substrate W.
  • a defect such as a change in the optical path of the exposure light EL due to foreign matters such as particles adhering to the second film Tc occurs on the substrate W.
  • There is a possibility of exposure failure such as a defect in the pattern to be performed.
  • the foreign matter adhering to the second film Tc includes a watermark.
  • the exposure failure of the substrate P exposed through the liquid LQ is analyzed, and the cause of the exposure failure is specified.
  • step SA30 After the exposure processing (step SA30) of the substrate P via the liquid LQ is completed, the substrate P is subjected to beta processing (post-beta) (step SA40). Then before development A first measurement process for measuring an abnormality of the substrate P is performed (step SA50).
  • the abnormality of the second film Tc on the substrate P after exposure and before development is measured, the position where the abnormality occurs is specified, and the abnormality is detected.
  • An image (optical image) in the vicinity of the position where the occurrence occurs is acquired using a predetermined measuring device (defect inspection device).
  • the measuring device for example, a device described in the column of the related art or the embodiment of the invention in JP-T-2002-519667 can be used.
  • FIG. 13 is a schematic diagram for explaining an operation of measuring an abnormality of the substrate P using a predetermined measuring device.
  • a plurality of shot areas are set on the substrate P, and the measuring device measures the abnormality of the second film Tc on the substrate P before being developed.
  • the measurement apparatus has a predetermined measurement area MA, and acquires an image (optical image) of the substrate P surface (second film Tc) in the measurement area MA.
  • the measurement apparatus sets a coordinate system (XY coordinate system) on the surface of the substrate P, and moves each of the coordinate systems set on the substrate P while relatively moving the measurement area MA and the substrate P.
  • An image (optical image) of the second film Tc at the position is acquired. Then, for example, the images in the adjacent measurement areas MA are compared with each other, and the position where the abnormality occurs in the second film Tc is specified based on the comparison result.
  • the measuring device measures almost the entire surface of the substrate P.
  • an image of the vicinity of the position where an abnormality has occurred in the second film Tc on the substrate P, which is specified by the measurement device, is further accurately detected by a scanning electron microscope (SEM). Obtained at.
  • the measuring device outputs position information where an abnormality has occurred on the second film Tc to the scanning electron microscope.
  • the scanning electron microscope can efficiently acquire an image in the vicinity of a position where an abnormality has occurred based on the position information output from the measuring device.
  • the development process is performed on the substrate P (step S A60).
  • the substrate P is developed in the developer device of the coater / developer device CD.
  • the second film Tc is removed, and when the lHRg is a positive resist, the portion irradiated with the exposure light EL is removed. Note that when the lHRg is a negative type resist, the portion irradiated with the exposure light EL remains.
  • a pattern (wiring pattern) is formed on substrate P (base material W) by applying predetermined processing such as etching to substrate P. Is formed.
  • step SA70 a second measurement process for measuring an abnormality of the substrate P after being developed is performed (step SA70).
  • abnormalities on almost the entire area of the substrate P (base material W) are measured using the above-described measurement device (defect inspection device).
  • the measuring device identifies the position of the substrate P (base material W) where an abnormality (pattern defect, exposure failure) has occurred.
  • the scanning electron microscope (SEM) acquires an image of the substrate P (base material W) near the position where an abnormality has occurred.
  • Step SA80 an analysis process for analyzing an exposure failure of the substrate P exposed through the liquid LQ is performed based on the measurement result of the first measurement process and the measurement result of the second measurement process.
  • the cause of the exposure failure pattern defect
  • the measurement result of the first measurement process is identified based on the measurement result of the first measurement process and the measurement result of the second measurement process.
  • the cause of the exposure failure is a force force due to an abnormality of the second film Tc or a force force due to a foreign substance in the liquid LQ.
  • FIG. 14A an image as shown in FIG. 14A is obtained as an image near the position of the substrate P (second film Tc) on which the phenomenon occurs.
  • liquid LQ as shown in FIG. 7 is infiltrated, foreign matter is present inside the second film Tc as shown in FIG. 8, one of the second films Tc as shown in FIG. It is possible to cut half-way between the state where the part is peeled off and the state where foreign matter is adhered to the second film Tc as shown in FIG.
  • FIG. 14B shows an image of a state in which a part of the wiring pattern formed on the substrate P (base W) is broken or a pattern defect in which the line width is nonuniform occurs.
  • FIG. 15A there is no abnormality in the substrate P (second film Tc) before being developed
  • FIG. 15B the substrate P after being developed (base material W). If there is an abnormality (pattern defect), it can be determined that the cause of the pattern defect (exposure failure) of the substrate P is due to foreign matter (bubbles, particles) in the liquid LQ. The foreign matter in the liquid LQ does not affect the second film Tc and is not measured by the first measurement process.
  • the measurement results obtained by measuring the abnormality of the substrate P before being exposed and developed through the liquid LQ and the measurement results of measuring the abnormality of the substrate P after development are obtained. Based on! Thus, it can be determined whether the exposure failure (pattern defect) is caused by an abnormality of the second film Tc or an abnormality other than the abnormality of the second film Tc. If an abnormality of the substrate P (second film Tc) is detected in the first measurement process, determine that the cause of the exposure failure (pattern defect) is due to the abnormality of the second film Tc. If no abnormality is detected in the first measurement process and an abnormality (pattern defect) in the substrate P (base material W) is detected in the second measurement process, the cause of exposure failure (pattern defect) ) Is caused by foreign matter in the liquid LQ.
  • the control device 7 can set the exposure conditions based on the analysis result, and can expose the substrate P under the set exposure conditions.
  • the exposure condition is at least one of the immersion condition when the optical path space K of the exposure light EL is filled with the liquid LQ and the moving condition of the substrate P with respect to the optical path space K.
  • the immersion conditions include at least one of supply conditions for supplying the liquid LQ to fill the optical path space K of the exposure light EL and recovery conditions for recovering the liquid LQ.
  • the movement condition of the substrate P includes at least one of a movement speed, an acceleration (deceleration), a movement direction (movement locus), and a movement distance when moving in a predetermined direction.
  • the control device 7 In order to suppress the occurrence, for example, the immersion conditions when the optical path space K of the exposure light EL is filled with the liquid LQ are adjusted, or the movement conditions of the substrate P with respect to the optical path space K filled with the liquid LQ are adjusted. Specifically, for example, in order to suppress the generation of bubbles in the liquid LQ that forms the immersion region LR, the deaeration capacity of the deaeration device of the liquid supply device 11 is increased, or the optical path space K is supplied from the supply port 12 Adjust the amount of liquid supplied per unit time.
  • the liquid recovery amount per unit time through the recovery port 22 may be adjusted in order to suppress the generation of bubbles in the liquid LQ forming the liquid immersion region LR. Further, by adjusting the moving speed or acceleration of the substrate P with respect to the liquid LQ in the liquid immersion area LR, the generation of bubbles in the liquid LQ forming the liquid immersion area LR can be suppressed. In addition, by adjusting the contact angle between the liquid contact surface of the substrate P (i.e., the second film Tc) and the liquid LQ, it is possible to suppress the generation of bubbles in the liquid LQ that forms the immersion region LR. it can.
  • the material of the second film Tc is reselected.
  • Appropriate measures can be taken, such as adjusting the coating conditions when coating the second film Tc with a coating device.
  • the contact time between the second film Tc and the liquid LQ can be adjusted to suppress the occurrence of abnormality in the second film Tc. There is a possibility.
  • the abnormality of the substrate P after exposure is measured.
  • measurement of abnormality of the substrate P before exposure is added. That is, in FIG. 16, first, the abnormal force of the substrate (wafer) W before exposure is measured using the above-described measuring device (defect inspection device) or the like (step SA1). Next, for example, an antireflection film is applied on the substrate W (step SA2), and the abnormality of the antireflection film is measured (step SA3). Next, the first lHRg, which is also a photosensitive material, is applied on the antireflection film (step SA10), and the abnormality of the first HRg is measured (step SA15).
  • a second film Tc serving as a top coat film is applied on the lHRg (step SA20), and the abnormality of the second film Tc is measured (step SA25). Then, exposure of the substrate P (step SA30), post-beta processing for the exposed substrate P (step SA40), first measurement processing (step SA50), development (step SA60), and second measurement processing (step SA70) and analysis processing (step SA80) are sequentially performed.
  • the second measurement in which the abnormality is detected in the first measurement process for measuring the substrate P before being developed, and the substrate P after being developed is measured. If an abnormality is detected in the measurement process, it is determined that the cause of the exposure failure is due to an abnormality in the second film Tc. In the first and second embodiments, no abnormality is detected in the first measurement process for measuring the substrate P before development, and an abnormality is detected in the second measurement process for measuring the substrate P after development. If is detected, it is determined that the cause of the exposure failure is due to foreign matter in the liquid LQ.
  • an abnormality is detected in the first measurement process for measuring the substrate P before being developed, and an abnormality is detected in the second measurement process for measuring the substrate P after being developed.
  • the immersion area LR is formed on the first shot area S1, and the liquid LQ of the immersion area LR is formed.
  • the abnormality is ineffective, but other shot regions (for example, adjacent to the first shot region S1)
  • the shot area S2, S6, S7, S8, etc.) the liquid in the immersion area LR that covers these other shot areas LQ may contact the first shot area SI.
  • the second film Tc in the first shot region S1 will be in contact with the liquid LQ for a long time, and as shown in FIGS. 6 and 7, the liquid LQ may penetrate into the second film Tc. There is. That is, when the exposure light EL is irradiated to the first shot region S1, the first shot region S1 having no abnormality in the second film Tc of the first shot region S1 causes an exposure failure.
  • an abnormality may occur in the second film Tc in the first shot region S1 after the exposure is completed.
  • an abnormality in the second film Tc in the first shot area S1 is detected in the first measurement process, but the first shot area is detected in the second measurement process. Abnormality of substrate W of S1 is not detected.
  • the intrusion (penetration) of the liquid LQ does not occur and the time in contact with the liquid LQ is the predetermined time. If this is the case, it can be determined that liquid LQ intrusion (penetration) occurs. Therefore, exposure conditions can be set and the second film Tc can be reselected in consideration of the predetermined time.
  • the abnormality of the substrate P is measured by the measurement device (defect inspection device) for the first measurement process and the second measurement process, and The position where the abnormality occurs is identified, and the image near the position is obtained with a scanning electron microscope with higher accuracy.
  • the scanning electron is not necessarily used. Any configuration that does not require the use of a microscope can be employed.
  • the substrate P has a second film (topcoat film) Tc that covers the first lHRg made of a photosensitive material formed on the base material W.
  • the second film Tc may be omitted. In that case, the abnormality of the first film Rg on the substrate P before development is measured in the first measurement process, and the abnormality of the substrate P after development is measured in the second measurement process.
  • the film on the outermost layer of the substrate P (the second film Tc or the first film) is based on the receding contact angle ⁇ of the liquid LQ on the surface of the substrate P.
  • HRg is to judge whether the film has few exposure defects (pattern defects).
  • the receding contact angle ⁇ will be described with reference to the schematic diagram of FIG. Receding contact angle ⁇ and
  • the liquid LQ droplet is attached to the surface of the object (here, the surface of the substrate P) and the surface of the object is inclined with respect to the horizontal plane, it adheres to the surface of the object.
  • the receding contact angle ⁇ is the thing with liquid LQ droplets attached
  • the receding contact angle ⁇ is easily measured using a known measuring device.
  • the inventor of the present application performs immersion exposure on a plurality of substrates, each having a film made of a different material on the outermost layer, and uses the method described in the first embodiment and the second embodiment.
  • Pattern defect (exposure failure) of each pattern and the pattern defect level (including at least one of defect density and number of defects) of each substrate ⁇ was inspected.
  • the defect level differs depending on R. More specifically, the inventor of the present application indicates that the larger the receding contact angle ⁇ of the liquid LQ on the surface of the substrate, the higher the defect level.
  • FIG. 18 shows the relationship between the receding contact angle 0 of the liquid LQ on the substrate surface and the defect level.
  • FIG. 18 shows points corresponding to the above-described inspection results of each substrate board and approximate curves obtained by fitting these inspection results. As shown in Figure 18, the receding contact angle ⁇ increases
  • the defect level (defect density, number of defects, etc.) of the substrate surface after immersion exposure can be estimated, and it is a film suitable for device pattern formation using the immersion exposure method. It can be judged whether there is a certain force. From Fig. 18, receding contact angle ⁇ force, for example, about 70 degrees or more It can be seen that it is desirable to use the top membrane.
  • the receding contact angle ⁇ may be used as an index for selecting the outermost layer film of the substrate P.
  • the exposure condition of the substrate P is determined.
  • the exposure conditions include the movement condition of the substrate p and the Z or immersion conditions (including at least one of the supply amount and recovery amount of the liquid LQ). For example, if exposure defects (pattern defects) are reduced by changing the speed of the substrate P, the receding contact angle ⁇
  • the moving speed during the scanning exposure of the substrate P can be set so that the exposure failure (pattern defect) is reduced. Note that the receding contact angle of the substrate P is determined only by the moving speed of the substrate P.
  • the exposure defect depends on the receding contact angle ⁇ .
  • the supply amount (and Z or recovery amount) of the liquid LQ may be set so that the (defects) may decrease.
  • pure water is used as the liquid LQ.
  • Pure water has the advantage that it can be easily obtained in large quantities at semiconductor manufacturing sites, etc., and has no adverse effect on the photoresist on the substrate P and optical elements (lenses).
  • pure water has no adverse effects on the environment, and the impurity content is extremely low, so it is expected to clean the surface of the substrate P and the surface of the optical element provided on the front end surface of the projection optical system PL. it can.
  • the exposure apparatus may have an ultrapure water production device.
  • the refractive index n of pure water (water) for exposure light EL with a wavelength of about 193 nm is approximately 1.44.
  • ArF excimer laser light wavelength: 193 nm
  • the wavelength is reduced to lZn, that is, about 134 nm, and high resolution can be obtained.
  • the projection optical system PL can be used when the same depth of focus as that in the air can be secured.
  • the numerical aperture can be increased further, and the resolution is improved in this respect as well.
  • the optical element FL is attached to the tip of the projection optical system PL, and the optical characteristics of the projection optical system PL such as aberration (spherical aberration, coma aberration, etc.) are adjusted by this optical element. It can be carried out.
  • the optical element attached to the tip of the projection optical system PL may be an optical plate used for adjusting the optical characteristics of the projection optical system PL. Or it may be a plane parallel plate (such as a cover glass) that can transmit the exposure light EL.
  • the space between the projection optical system PL and the surface of the substrate P is filled with the liquid LQ.
  • a cover made of a plane parallel plate on the surface of the substrate P for example. It may be configured to fill the liquid LQ with the glass attached.
  • the optical path space on the image plane side of the optical element at the tip of the projection optical system is filled with liquid, but as disclosed in International Publication No. 2004Z019128, the tip optical It is possible to adopt a projection optical system that fills the optical path space on the object plane side of the element with liquid.
  • liquid LQ in each of the above embodiments is water, but may be a liquid other than water! /,
  • the light source of the exposure light EL is an F laser
  • this F laser light Does not pass water
  • PFPE perfluoropolyether
  • a fluorinated fluid such as fluorinated oil
  • the portion that comes into contact with the liquid LQ is made lyophilic by, for example, forming a thin film with a substance having a small molecular structure including fluorine.
  • the liquid LQ is stable against the photoresist applied to the projection optical system PL and the substrate P, which is transparent to the exposure light EL and has a refractive index as high as possible (for example, Cedar). Oil) is also possible [0088]
  • a liquid having a refractive index of about 1.6 to 1.8 may be used.
  • the optical element FL may be formed of a material having a refractive index higher than that of quartz or fluorite (for example, 1.6 or more).
  • the substrate P in each of the above embodiments not only a semiconductor wafer for manufacturing a semiconductor device, but also a glass substrate for a display device, a ceramic wafer for a thin film magnetic head, a mask used in an exposure apparatus, or Reticle masters (synthetic quartz, silicon wafers) are applied.
  • a step-and-scan type scanning exposure apparatus in addition to the scanning steno, mask M It can also be applied to a step-and-repeat projection exposure apparatus (steno) in which the pattern of the mask M is collectively exposed while the substrate P is stationary and the substrate P is moved stepwise.
  • a reduced image of the first pattern is projected with the first pattern and the substrate P substantially stationary, for example, a refractive optical system that does not include a reflective element at a 1Z8 reduction magnification. It can also be applied to an exposure apparatus that uses a projection optical system) to perform batch exposure on the substrate P. In this case, after that, with the second pattern and the substrate P almost stationary, a reduced image of the second pattern is collectively exposed on the substrate P by partially overlapping the first pattern using the projection optical system. It can also be applied to a stitch type batch exposure apparatus. In addition, the stitch type exposure apparatus can also be applied to a step 'and' stitch type exposure apparatus in which at least two patterns are partially overlapped and transferred on the substrate P, and the substrate P is sequentially moved.
  • the exposure apparatus provided with the projection optical system PL has been described as an example.
  • the present invention is applied to an exposure apparatus and an exposure method that do not use the projection optical system PL. Can do. Even when the projection optical system is not used, the exposure light is irradiated onto the substrate through an optical member such as a mask or a lens, and an immersion region is formed in a predetermined space between the optical member and the substrate.
  • an optical member such as a mask or a lens
  • JP-A-11-135400 corresponding international publication 1999/23692
  • JP-A 2000-164504 corresponding US Pat. No. 6,897,963
  • the present invention can also be applied to an exposure apparatus including a substrate stage for holding a substrate, a reference member on which a reference mark is formed, and a measurement stage on which various photoelectric sensors are mounted.
  • an exposure apparatus that locally fills the liquid between the projection optical system PL and the substrate P is employed.
  • the present invention is disclosed in, for example, Japanese Patent Laid-Open No. 6-124873.
  • Liquid exposure light that performs exposure in a state where the entire surface of the substrate to be exposed is immersed in a liquid as disclosed in JP-A-10-303114, US Pat. No. 5,825,043, etc. It is also applicable to the device.
  • the type of exposure apparatus EX is not limited to an exposure apparatus for manufacturing a semiconductor element that exposes a semiconductor element pattern onto a substrate P, but an exposure apparatus for manufacturing a liquid crystal display element or a display, a thin film magnetic head, an imaging device It can be widely applied to exposure devices for manufacturing devices (CCD), micromachines, MEMS, DNA chips, reticles or masks.
  • a light-transmitting mask in which a predetermined light-shielding pattern (or phase pattern 'dimming pattern) is formed on a light-transmitting substrate.
  • a predetermined light-shielding pattern or phase pattern 'dimming pattern
  • an electronic mask (variable molding mask) that forms a transmission pattern, a reflection pattern, or a light emission pattern based on electronic data of a pattern to be exposed.
  • a DMD Digital Micro-mirror Device
  • spatial light modulator spatial light modulator
  • an exposure apparatus that exposes a line “and” space pattern on the substrate P by forming interference fringes on the substrate P (lithography)
  • the present invention can also be applied to a system.
  • the exposure apparatus EX provides various mechanical systems including the respective constituent elements recited in the claims of the present application with predetermined mechanical accuracy, electrical accuracy, and optical accuracy. Manufactured by assembling to keep. In order to ensure these various accuracies, before and after the assembly, various optical systems are adjusted to achieve optical accuracy, various mechanical systems are adjusted to achieve mechanical accuracy, various electrical systems Is adjusted to achieve electrical accuracy.
  • the assembly process from various subsystems to the exposure system includes mechanical connections, electrical circuit wiring connections, and pneumatic circuit piping connections between the various subsystems. Needless to say, there is an assembly process for each subsystem before the assembly process from the various subsystems to the exposure apparatus. When the assembly process of the various subsystems to the exposure apparatus is completed, comprehensive adjustment is performed to ensure various accuracies for the entire exposure apparatus. It is desirable to manufacture the exposure apparatus in a clean room in which the temperature and cleanliness are controlled.
  • a microdevice such as a semiconductor device includes a step 201 for performing a function / performance design of the microdevice, a step 202 for manufacturing a mask (reticle) based on the design step, Step 203 of manufacturing a substrate as a base material, a step of exposing the mask pattern to the substrate by the exposure apparatus EX of the above-described embodiment, a step of developing the exposed substrate, a heating (curing) of the developed substrate, and an etching step
  • the substrate is manufactured through a step 204 including a substrate processing process, a device assembly step (including processing processes such as a dicing process, a bonding process, and a knocking process) 205, an inspection step 206, and the like.

Landscapes

  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Exposure Of Semiconductors, Excluding Electron Or Ion Beam Exposure (AREA)
  • Exposure And Positioning Against Photoresist Photosensitive Materials (AREA)
  • Analysing Materials By The Use Of Radiation (AREA)

Abstract

L’invention concerne un procédé d’analyse qui comporte une étape (SA60) consistant à développer un substrat, une première étape de mesure (SA50) consistant à mesurer une anomalie du substrat avant qu’il ne soit développé, une seconde étape de mesure (SA70) consistant à mesurer une anomalie du substrat développé, et une étape (SA80) consistant à analyser un défaut d’exposition du substrat exposé à travers un liquide, sur la base des résultats des mesures de la première étape de mesure (SA50) et de la seconde étape de mesure (SA70).
PCT/JP2006/317901 2005-09-09 2006-09-08 Procédés d'analyse, d’exposition et de fabrication de dispositif WO2007029828A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP2007534489A JP4992718B2 (ja) 2005-09-09 2006-09-08 解析方法、露光方法及びデバイス製造方法

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
JP2005261887 2005-09-09
JP2005-261887 2005-09-09

Publications (1)

Publication Number Publication Date
WO2007029828A1 true WO2007029828A1 (fr) 2007-03-15

Family

ID=37835942

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/JP2006/317901 WO2007029828A1 (fr) 2005-09-09 2006-09-08 Procédés d'analyse, d’exposition et de fabrication de dispositif

Country Status (3)

Country Link
JP (1) JP4992718B2 (fr)
TW (1) TWI430040B (fr)
WO (1) WO2007029828A1 (fr)

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004200680A (ja) * 2002-11-01 2004-07-15 Asml Netherlands Bv 検査方法およびデバイス製造方法
JP2005142576A (ja) * 2003-10-17 2005-06-02 Asml Netherlands Bv リソグラフィ処理セル、リソグラフィ装置、トラック、及びデバイス製造法
JP2006222284A (ja) * 2005-02-10 2006-08-24 Toshiba Corp パターン形成方法、及び半導体装置の製造方法
JP2006243264A (ja) * 2005-03-02 2006-09-14 Fuji Photo Film Co Ltd 液浸露光用ポジ型レジスト組成物及びそれを用いたパターン形成方法
JP2006253501A (ja) * 2005-03-11 2006-09-21 Tokyo Electron Ltd 塗布、現像装置及びその方法

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
AU2003220830A1 (en) * 2002-03-12 2003-09-22 Olympus Corporation Semiconductor manufacturing method and device thereof

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2004200680A (ja) * 2002-11-01 2004-07-15 Asml Netherlands Bv 検査方法およびデバイス製造方法
JP2005142576A (ja) * 2003-10-17 2005-06-02 Asml Netherlands Bv リソグラフィ処理セル、リソグラフィ装置、トラック、及びデバイス製造法
JP2006222284A (ja) * 2005-02-10 2006-08-24 Toshiba Corp パターン形成方法、及び半導体装置の製造方法
JP2006243264A (ja) * 2005-03-02 2006-09-14 Fuji Photo Film Co Ltd 液浸露光用ポジ型レジスト組成物及びそれを用いたパターン形成方法
JP2006253501A (ja) * 2005-03-11 2006-09-21 Tokyo Electron Ltd 塗布、現像装置及びその方法

Also Published As

Publication number Publication date
TWI430040B (zh) 2014-03-11
TW200715069A (en) 2007-04-16
JPWO2007029828A1 (ja) 2009-03-19
JP4992718B2 (ja) 2012-08-08

Similar Documents

Publication Publication Date Title
JP4888388B2 (ja) 露光方法、露光装置、及びデバイス製造方法
JP5239337B2 (ja) 露光方法及び露光装置、並びにデバイス製造方法
JP4852951B2 (ja) 露光装置、露光方法及びデバイス製造方法
WO2007004552A1 (fr) Appareil et procédé d'exposition, procédé d'entretien de l'appareil d'exposition, et procédé de fabrication de dispositif
WO2006106832A1 (fr) Procede pour determiner des conditions d’exposition, procede d’exposition, dispositif d’exposition, et appareil de production du dispositif
WO2006101024A1 (fr) Procédé d’exposition, appareil d’exposition, procédé de fabrication de dispositif et procédé d’évaluation d’appareil d’exposition
WO2007001045A1 (fr) Appareil d'exposition, procédé de traitement d'un substrat et procédé de fabrication du dispositif
US20080117401A1 (en) Surface treatment method and surface treatment apparatus, exposure method and exposure apparatus, and device manufacturing method
JP4544303B2 (ja) 露光装置及び露光方法、並びにデバイス製造方法
JPWO2010050240A1 (ja) 露光装置、露光方法、及びデバイス製造方法
US8111374B2 (en) Analysis method, exposure method, and device manufacturing method
JP2007287824A (ja) 露光装置及びデバイス製造方法
JP2007116073A (ja) 露光方法及び露光装置、並びにデバイス製造方法
JP2010040702A (ja) ステージ装置、露光装置、及びデバイス製造方法
JP5229264B2 (ja) 露光装置、露光方法及びデバイス製造方法
JP4752374B2 (ja) 露光装置、液体保持方法、及びデバイス製造方法
WO2007000995A1 (fr) Appareil et procédé d'exposition, ainsi que procédé de fabrication de l'appareil
WO2008075742A1 (fr) Méthode d'entretien, méthode d'exposition, dispositif d'exposition et méthode de fabrication du dispositif
JP4992718B2 (ja) 解析方法、露光方法及びデバイス製造方法
JP5045008B2 (ja) 液浸露光用基板、露光方法及びデバイス製造方法
JP4992558B2 (ja) 液浸露光装置、デバイス製造方法、及び評価方法
JP2010109271A (ja) 確認方法、メンテナンス方法、及びデバイス製造方法
WO2007007723A1 (fr) Substrat pour une exposition par immersion, procédé d'exposition et procédé pour fabriquer un dispositif
JP2010109270A (ja) 確認方法、メンテナンス方法、及びデバイス製造方法
JP2008205460A (ja) 決定方法、評価方法、露光方法、評価装置、液浸露光装置、及びデバイス製造方法

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application
ENP Entry into the national phase

Ref document number: 2007534489

Country of ref document: JP

Kind code of ref document: A

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 06797727

Country of ref document: EP

Kind code of ref document: A1